Band 11, Heft 7

Oscillating chemical reactions, which are far from equilibrium, are extremely sensitive to certain species and may provide new analytical methods using the regular oscillations as well as the non-equilibrium stationary state after system bifurcation. This review of their application to analytical chemistry from 2005 to 2012 includes other appropriate references. Both organic and inorganic analytes are included.

An amorphous complex of Tb(III) with the biscoumarin derivative 3,3′-[(4-hydroxyphenyl)methylene)]bis-(4-hydroxy-2H-1-benzopyran-2-one), Tb(H2L)3, was successfully synthesized and characterized. IR- and 1H-NMR-spectroscopy were used to investigate the coordination of the ligand around the Tb(III) ion. Values for the quantum yield and the life time of the excited state of the complex were obtained. The complex was immobilized in transparent and flexible PMMA-based films by a simple casting technique. PMMA/chloroform solutions were used in synthetic procedures that resulted in both glass-supported and self-supporting nanocomposite films. The morphology of the films was studied by scanning electron microscopy, atomic force microscopy and transmission electron microscopy, showing the formation of crack-free films. The presence of the Tb(III) complex in the matrix was proven by the presence of characteristic bands in the IR spectra. Fluorescence microscopy and fluorescence spectroscopy demonstrated the promising optical properties of the films showing the characteristic emission bands of the Tb(III) ions. The longer life time of the excited state of the immobilized complex confirmed the protective role of the PMMA matrix on the optical properties of the complex. The composite films possessing optical properties have the potential for application as active components in optical devices.

In the current work, iron oxide magnetic nanoparticles (MNP’s) were synthesized by thermal decomposition of Fe(acac)3-(iron acetylacetonate) compounds in high-boiling organic solvents containing stabilizing surfactants and examined as possible agents for magnetic hyperthermia treatment, according to their structural, magnetic and heating properties. Three different cancer cell lines (DA3, MCF-7 and HeLa cell lines) were used to assess the suitability of the MNP’s. The experimental results proved that the synthesized MNPs are non-toxic and the uptake efficiency was extremely good. Further, from in vitro hyperthermia results, very fast thermal response was observed (reaching hyperthermia levels in less than 200 s), which minimize the duration of the cell and human body exposure in a high frequency AC external magnetic field.

For the first time a combination of microwaves and/or the conventional treatment method was used to dry and heat multilayered sol-gel ZnO/TiO2/glass structures. Compact or porous TiO2 films were deposited as a bottom layer, covered with a ZnO film. The structures were characterized by X-ray Diffraction (XRD), Energy Dispersive X-ray Spectroscopy (EDX) and Scanning Electron Microscopy (SEM). Only peaks of wurtzite ZnO crystalline phase were registered on the X-Ray diffractograms. The microwave irradiation leads to a formation of poorly crystallized multilayers with very small crystallites and enhanced surface roughness. This results in a better photocatalytic activity of these structures than the structures of the samples treated conventionally. It was established that the morphology of the bottom titania layer affects the reaction of photocatalytic degradation of Malachite Green dye (MG). The structures with the compact bottom TiO2 films showed higher activities than those on porous TiO2 films. This study offers an energy saving method of producing ZnO/TiO2/glass multilayered structures of various morphologies and pronounced photocatalytic properties. The method does not involve any calcination step, normally applied to achieve a good degree of crystallization. This makes the method suitable for protecting substrates of low thermal stability.

Packaging based on immobilization of antimicrobial enzymes provides a promising form of active packaging systems applicable in food processing. Glucose oxidase and lysozyme were immobilized by the Ugi reaction with cyclohexyl isocyanide and glutaraldehyde on polyamide and ionomer films partially hydrolysed by hydrochloric acid. The immobilization of the enzymes on the surface of films was confirmed by FT-IR spectroscopy and the films were characterized by the specific activity of the immobilized enzymes. The enzyme migration into model solutions and the effect of pH, temperature and storage time on the activity of immobilized enzyme were also evaluated. Immobilization of lysozyme onto polyamide and ionomer films resulted in the loss of enzyme activity. The polyamide and ionomer films with immobilized glucose oxidase inhibited the growth of bacteria Escherichia coli CNCTC 6859, Pseudomonas fluorescens CNCTC 5793, Lactobacillus helveticus CH-1, Listeria ivanovii CCM 5884 and Listeria innocua CCM 4030 on agar media.

Oxidatively generated damage to DNA frequently appears in the human genome as the effect of aerobic metabolism or as the result of exposure to exogenous oxidizing agents such as ionization radiation. In this paper, for the first time, the electronic properties of nucleoside pairs containing 5′,8-cyclo-2′-deoxyadenosine (cdA) in their 5′R and 5′S diastereomeric forms (cdA(R)::T and cdA(S)::T) as the simplest model of ds-DNA have been discussed. The following values of the selected electronic parameters, measured in eV, were found for cdA(R)::T, cdA(S)::T, and dA::T, respectively, adiabatic/vertical electron affinity: 0.39/0.24, 0.35/0.18, 0.33/0.21; and adiabatic/vertical ionization potential: 7.27/7.50, 7.7.25/7.49, 7.03/7.27. Moreover, based on the results of the relaxation energy, the presence of cdA(S)::T should provide the highest barrier for electron transfer in ds-DNA. Analyses of hydrogen bond length deviations reveal that the formation of cationic forms results in higher elongation than that of anionic forms. Moreover, during the electron attachment or detachment for the investigated cdA(R)::T, cdA(S)::T, and dA::T nucleoside pairs, the same scheme of changes in hydrogen bond length was noted.

In this work attention is focused on impurity profile analysis in combination with infrared spectroscopy and chemometric methods. This approach is considered as an alternative to generally complex and time-consuming classic analytical techniques such as liquid chromatography. Various strategies for constructing descriptive models able to identify relations among drug impurity profiles hidden in multivariate chromatographic data sets are also presented and discussed. The hierarchical (cluster analysis) and non-hierarchical segmentation algorithms (k-means method) and principal component analysis are applied to gain an overview of the similarities and dissimilarities among impurity profiles of acetylsalicylic acid formulations. A tree regression algorithm based on infrared spectra is used to predict the relative content of impurities in the drug products investigated. Satisfactory predictive abilities of the models derived indicate the possibility of implementing them in the quality control of drug products.

Protonation constants of protonated monomers and dimers of the vildagliptin are determined potentiometrically. For the low concentration c L = 3.3 mmol dm−3 the monomers L and LH dominate, while for a higher concentration c L = 6.3 mmol dm−3 the dimers L2H2, L2H3, L2H4 and L2H are mainly present. The algorithm used has little influence on the precision of the formation constants in comparison with the reproducibility of the titration. The mixed protonation constants of vildagliptin dimers Lq Hr at various temperatures are determined using FBSTAC4 and HYPERQUAD regression analysis of the potentiometric titration data. The accuracy of the protonation constants log10 βqr depends on the accuracy of the group parameters. As two group parameters L 0, H T are ill conditioned in a model, their determination is therefore uncertain; both can significantly cause a systematic error in the estimated common parameters log10 βqr . Using various regression diagnostics the goodness-of-fit proves the reliability of all parameter estimates. A rough estimation of thermodynamic enthalpies ΔH 0 (kJ mol−1) and entropies ΔS 0 (J K−1 mol−1) is determined from the temperature variation of protonation constants. The enthalpy shows the protonation process is exothermic, and the entropy indicates that it is spontaneous.

One of the quantification methods frequently applied to pesticide residue analysis in food by liquid chromatography — mass spectrometry (LC-MS) involves matrix-matched calibrations with a representative matrix used for all commodities belonging to one group. This approach, although very practical, is deemed to generate analytical errors. The effect of the application of a representative-matrix calibration curve on the pesticide quantification result was examined. Extractions of 56 pesticides from five soft fruits (strawberries, blackberries, raspberries, black currant and red currant) were carried out using QuEChERS method. Pesticide determinations were performed by LC-MS/MS in multiple reaction monitoring mode. Quantification difference functions and parameters were proposed and calculated. At the concentration of 0.05 mg kg−1 for ca. 90% of examined pesticides the quantification difference arising from the use of a representative matrix calibration curve (raspberries) instead of a specific fruit matrix calibration curve was below 20% for black and red currents, and below 30% and 35% in the case of strawberries and blackberries, respectively. The 25% difference limit was not exceeded for 51 pesticides in black and red currents, 46 pesticides in blackberries and 45 pesticides in strawberries. Quantification difference functions and parameters such as relative standard deviation of corrected process efficiencies were found to be helpful in data-driven decision-making on the applicability of a representative matrix; the former may be also used as a tool for data correction to ensure the reliability and accuracy of analyses.

This study was focused on the investigation of novel hybrid organo/inorganic systems for oxygen sensing applications. As a host material, a synthetic clay mineral Sumecton SA was chosen, while, as guest materials, metalloporphyrins containing Pt(II) and Pd(II) were chosen. These are known to be very efficient agents for sensing applications because of a “heavy atom effect”. This effect promotes a spin-orbit coupling, resulting in the fact that almost all of the radiation from a singlet excited state undergoes intersystem crossing, followed by a de-excitation via a triplet state. The combination of metalloporphyrin and layered materials enables unique oxygen sensing properties due to the steric effects of layered materials. The result is that the emission from the membrane was sensitive at the range around aerobic conditions. The spectroscopic analysis of hybrid systems — clay/porphyrin membranes (CPMs) showed that these materials can serve as prospective candidates for the construction of effective, reliable and economical oxygen sensors.

Thin films of Zn-Ni-P on a copper substrate were synthesized by electrodeposition from chloride baths. It was found that the diffraction reflections of the crystal structure of Zn-Ni-P thin layers occur at thicknesses d ≥ 5 µm. The X-ray diffraction studies results confirm the formation in the Zn-Ni-P films of ZnNi10P3 compound. The morphology of the obtained films was analyzed by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectrometry (EDS). The films are continuous and have a typical topography with many homogeneous globular features. EDS confirmed the formation of Zn-Ni-P coating only in 2 samples with Zn:Ni:P atomic ratios of 1:8:4 and 4:8:3, respectively. X-ray Photoelectron Spectroscopy (XPS) revealed the chemistry and the thickness of the studied thin films. At room temperature and thickness d ≥ 5 µm the investigated thin layers exhibit high values of the specific magnetizations in the range (25–37) A m2 kg−1, leading to the potential use in devices, appliances and electronics. The Curie temperature values of the synthesized Zn-Ni-P films were determined. It was found that by heating Zn-Ni-P thin layers of thicknesses d ≥ 5 µm up to a temperature T=900 K an interaction was detected with the copper substrate leading to a lower specific magnetization.

Five different columns (two silica, two cyanopropyl and one diol) were investigated in hydrophilic interaction liquid chromatography (HILIC). For the assessment of columns behavior in HILIC mode, six basic drugs (lamotrigine, thioridazine, clozapine, chlorpheniramine, pheniramine and sulpiride) were chosen. The assessment of the influence of the concentration of organic modifier on analytes’ retention on each column was provided by fitting the retention data into theoretical models. Utilizing the statistical analysis, the selection of the model that provides better prediction of the retention behavior was enabled. Dual RP-HILIC mechanism was suggested on cyanopropyl and diol columns, therefore the transition points between the two mechanisms on these columns were calculated. Furthermore, in order to investigate the impact of three factors simultaneously on the retention behavior of the analyzed substances on Betasil Silica column, chemometrically-aided empirical models were built. The experiments were conducted according to the matrix of Box-Behnken design and on the basis of the retention data, six quadratic models were obtained and their adequacy was confirmed using ANOVA test. The obtained coefficients of quadratic models enabled the elucidation of both single factor and factor interactions influence. This was also graphically presented in 3D response surface plots.

The preparative conditions were optimized to get chalcogens layers on the polymer — polyamide PA surface by sorption at room temperature using sodium telluropentathionate, Na2TeS4O6. Further interaction of chalcogenized dielectric with copper’s (I/II) salt solution leads to the formation of mixed CuxSy-CuxTey layers. Optical, electrical and surface characteristics of the layers are highly controlled by the deposition parameters. The stoichiometry of these layers was established by UV-Visible and AA spectrometry. Optical absorption (transmittance) experiments show the samples are of high optical quality. The band gaps of thin films were obtained from their optical absorption spectra, which were found in the range of 1.44–2.97 eV. XRD was used in combination with AFM to characterize chalcogenides layers’ structural features. XRD analysis confirmed the formation of mixed copper chalcogenides’ layers in the surface of PA with binary phases such as Cu2Te, Cu3.18Te2, copper telluride, Cu2.72Te2, vulcanite, CuTe, anilite, Cu7S4 and copper sulfide, Cu1.8S. The crystallite sizes of thin films calculated by the Scherer formula were found to be in the range of 3.07–13.53 nm for CuxSy crystallites and 4.06–20.79 nm for CuxTey crystallites. At room temperature an electrical resistance of CuxSy-CuxTey layers varies from 3.0×103 kΩ□−1 to 1.0 kΩ□−1.

Room temperature 1-butyl-3-methylimidazolium tetraflouroborate ([BMIM][BF4]) ionic liquid was employed for dispersion of multi walled carbon nanotubes (MWCNTs) and the formation of nanocomposite on the surface of a carbon-ceramic electrode. The surface of the modified electrode was characterized using scanning electron microscopy and electrochemical impedance spectroscopy. The modified electrode exhibited excellent electrochemical activity to oxidation of dopamine (DA); whereas electro oxidation of ascorbic acid (AA) was not seen and electro oxidation of uric acid (UA) appeared at a more positive potential than DA. The multi walled carbon nanotube-ionic liquid nanocomposite modified carbon-ceramic electrode was used for the selective determination of DA in the presence of high levels of AA and UA using differential pulse voltammetry. The calibration curve for DA was linear in the range of 3.00 to 130 µM with the detection limit (S/N=3) of 0.87 µM. The present electrode was successfully applied to the determination of DA in some commercial pharmaceutical samples and human blood serum.

The CO2 gasification of a low rank coal catalysed by K2CO3 was studied, at 700–950°C and 1 atm. A two level full factorial design revealed that the gasification reaction was sensitive to the solid residence time, reaction temperature, CO2 partial pressure and catalyst load. K2CO3 was an efficient catalyst at all temperatures studied, particularly during the second stage when the Boudouard reaction dominates. The gasification rate was increased continuously with increasing catalyst load up to a load of ∼20% w/w K2CO3 concentration, following a sigmoid curve. Above this point, limited catalytic effect was observed, possibly due to the saturation of the lignite surface by K+. A correlation was found to exist between the catalytic gasification rate and the Alkali Index, which increased with the impregnation of the inorganic K2CO3 salt. When K2CO3 load increased, the Arrhenius parameters, E and k 0, increased simultaneously exhibiting a compensation effect. The isokinetic temperature was found about 600 to 650°C corresponding to the minimum temperature required for the formation of catalytic active intermediates. At temperatures studied, the catalytic active intermediates seemed to be always present and the catalysis progresses unhindered due to the redox cycle, resulting in high rates and conversion.

Application of economically important and time saving pretreatment for the screening element mobility evaluation of contaminated sediments is presented. Ultrasonically-assisted single-step extraction (USAE) was carried out by EDTA solution. The extraction time of USAE was optimized and obtained results were compared with results estimated by conventional (EDTA extraction) and by sequential extraction (modified BCR protocol). The original three step BCR protocol was modified by addition of the first step (water leaching) and the fifth step, total digestion of sediment residue (acid mixture with HF). Zn, Cu and Pb have been determined in extracts by ICP-OES. Good conformity of the ultrasonically-extracted element contents and sum of contents, extracted during first three steps (water-soluble, acid-extractable, reducible — i.e., the most mobile fractions) of sequential extraction, was found. The sono-extraction reduced operating time of the first three steps of sequential extraction from 48 h to 15 min. Thus, USAE can serve as a rapid screening assessment of the mobile and potentially mobile element portions in sediments and other similar solid state environmental media. Analytical quality control was realized by comparison of the sums of element contents obtained at individual (five) extraction steps. Total element contents were also determined by an independent method (XRF).

An optimization methodology based on neural networks and genetic algorithms was developed and used to optimize a real world process — an electro-coagulation process involving three pollutants at different concentrations: kaolin (250–1000 mg L−1), Eriochrome Black T solutions (50–200 mg L−1), and oil/water emulsion (1500–4500 mg L−1). Feed-forward neural networks using heterogeneous combination of transfer functions were developed, leading to good results in the validation stage (relative error about 8%). The parameters of the process (concentration of pollutant, time, pH0, conductivity and current density) were optimized handling the genetic algorithm parameters, in order to obtain a maximum removal efficiency for each pollutant. Therefore, the optimization methodology combines neural networks as modeling tools with genetic algorithms as solving method. Validation of the optimization results using supplementary experimental data reveals errors under 11%.

The reaction of R3M (M=Ga, In) with HESiR′3 (E=O, S; R′3=Ph3, iPr3, Et3, tBuMe2) leads to the formation of (Me2GaOSiPh3)2(1); (Me2GaOSitBuMe2)2(2); (Me2GaOSiEt3)2(3); (Me2InOSiPh3)2(4); (Me2InOSitBuMe2)2(5); (Me2InOSiEt3)2(6); (Me2GaSSiPh3)2(7); (Et2GaSSiPh3)2(8); (Me2GaSSiiPr3)2(9); (Et2GaSSiiPr3)2(10); (Me2InSSiPh3)3(11); (Me2InSSiiPr3)n(12), in high yields at room temperature. The compounds have been characterized by multinuclear NMR and in most cases by X-ray crystallography. The molecular structures of (1), (4), (7) and (8) have been determined. Compounds (3), (6) and (10) are liquids at room temperature. In the solid state, (1), (4), (7) and (9) are dimers with central core of the dimer being composed of a M2E2 four-membered ring. VT-NMR studies of (7) show facile redistribution between four- and six-membered rings in solution. The thermal decomposition of (1)–(12) was examined by TGA and range from 200 to 350°C. Bulk pyrolysis of (1) and (2) led to the formation of Ga2O3; (4) and (5) In metal; (7)–(10) GaS and (11)–(12) InS powders, respectively.

The simple and quick calibration surfaces method has been applied to the quantitative analysis of water — ethanol — methanol mixtures. The refractive index, viscosity, boiling point, density, and position of the absorption band of the solvatochromic dye and the absorbance of the band corresponding to a particular wavelength were used as measured magnitudes which are functionally related to the quantitative composition of the mixture. The 3rd order surface equation was fitted to the experimental data via the multidimensional regression method. Various pairs of macroscopic features were tested to obtain the best results. To find the solution, the set of three equations were calculated, in which two equations were the mathematical description of particular macroscopic features; the third one resulted from the definition of mass fraction. The detection and determination limits as well as the error of the method were determined which proved that the refractive index and the density were the most adequate pair of macroscopic features.

The stannocanes of the type [O(CH2CH2S)2SnR2](R=Me1,Bun2,Ph3) have been synthesized in an improved method by the reaction of R2SnCl2 with 2, 2′-oxydiethanethiol O(CH2CH2SH)2 in molar ratio of 1:1 at the presence of sodium ethoxide in anhydrous ethanol. The reactions are carried out under inert atmosphere. These compounds have been extensively characterized by FT-IR, UV-Vis spectrophotometry, multi-nuclear (1H, 13C, 119Sn) NMR, elemental analysis and mass spectrometry. The obtained data clearly indicates that, there is a strong interaction between oxygen atom of the ligand as a donor and Sn atom of the organotin species as a Lewis acid acceptor. Therefore, the resulted dithiostannocanes possess a transannular secondary bonding and hypervalency at the central Sn atom which leads to an increase in the coordination number of tin from four to five-coordinated tin.

The original version of the article was published in Cent. Eur. J. Chem. 11(6) (2013) pp. 912–919. Unfortunately, the original version of this article contains a mistake in the Acknowledgement section. It should be written as “Partially financed from grant number 0680/B/H03/2011/40 and gratefully acknowledged. Paweł Mierczyński is a participant of START Programme.”